O,o-dialkyl-o-(1,2-diazolidin-ones-5-yl-3)-thionophosphates

ABSTRACT

1. A DIALKYLTHIONOPHOSPHORIC ESTER OF THE FORMULA   1-R3,3-(R1-O-P(=S)(-O-R2)-O-),4-R4,4-R5,5-(O=)-2-   R-CO-NH-Y-(1,4-PHENYLENE)-SO2-NH-CO-NH-R1   PYRAZOLINE   WHERE R1 AND R2 ARE IDENTICAL OR DIFFERENT AND EACH DENOTES LOWER ALKYL, R3 DENOTES HYDROGEN, LOWER ALKYL, PHENYL OR CHLOROPHENYL, R4 AND R5 ARE IDENTICAL OR DIFFERENT AND EACH DENOTES LOWER ALKYL, LOWER ALKOXYMETHYL, LOWER ALKOXYETHYL, OR TOGETHER DENOTE LOWER ALKOXYMETHYLENE OR PENTAMETHYLENE.

United States Patent ice 3,847,936 0,0-DlALKYL-0-I1,2-DIAZOLIDIN-0NES-5-YL-31- THIONOPHOSPHATES Heinrich Adolphi, Limbnrgerhof, Wolfram Dietsclie,

Allrip, Franz Merger, Frankenthal, Peter Beutel, Mannheim, and Rolf Huber, Ludwigshafen, Germany, assignors to Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen (Rhine), Germany N0 Drawing. Filed Dec. 7, 1972, Ser. No. 312,974 Claims priority, application Germany, Dec. 18, 1971, P 21 63 063.7 Int. Cl. C07f 9/16 US. Cl. 260-310 A 6 Claims ABSTRACT OF THE DISCLOSURE New and valuable 0,0-dialkylthionophosphoric esters having a strong insecticidal action, pesticides containing these compounds as active ingredients, and a process for controlling pests with these compounds. The esters are 0,0 dialkyl-O-[1,Z-diazolidin-ones-S-yl-3] thionophosphates which may be substituted in the 1-position by lower alkyl, phenyl or chlorophenyl. They may be further substituted in the 4-position by lower alkyl, lower alkoxymethyl, lower alkoxyethyl, lower alkoxymethylene or a hydrocarbon ring having 5 or 6 members including the carbon in the 4-position.

The present invention relates to new and valuable 0,0- dialkylthionophosphoric esters having a strong insecticidal action, pesticides containing these compounds as active ingredients, and a process for their production and use as pesticides.

It is known to use phosphoric ester derivatives as pesticides. However, they have a poor biological action.

We have now found that 0,0-dialkylthionophosphoric esters of the formula NNR R10 S \TILLO 0 where R and R are identical or different and each denotes lower alkyl (methyl, ethyl), R denotes hydrogen, lower alkyl (methyl, ethyl, n-propyl and isopropyl), aryl (phenyl) or chlorophenyl, and R and R are identical or dilferent and each denotes hydrogen, lower alkyl (methyl, ethyl, propyl, butyl), lower alkoxyalkyl (methoxymethyl, ethoxymethyl, methoxyethyl) or together denote alkoxymethylene (ethoxymethylene) or a hydrocarbon ring having several members (fiveor six-membered, for example, pentamethylene), have a good insecticidal action.

The new active ingredients may be prepared by reacting an 0,0dialkylthionophosphoric ester halide of the formula where R and R have the meanings given above and hal denotes a halogen atom (chlorine, bromine), with a pyrazolidinedione of the formula t? I H lit where R R and R have the above meanings, or with an alkali metal salt thereof.

3,847,936 Patented Nov. 12, 1974 The pyrazolidinediones may be prepared for instance analogously to the processes described in the literature (Helv. chim. acta, 36, 74, 1953) by reaction of unsubstituted or substituted malonic diesters with hydrazine or monoalkyl hydrazines and subsequent cyclization employing suitable condensing agents, e.g., sodium methylate, in accordance with the following equation:

ONa

N R5 COOR 2 R i 1 +Na0CH R4 COOR NHR: 4

R R and R have the above meanings, and R denotes lower alkyl. The pyrazolidinediones can be separated by adding acid to the sodium salts.

The unsubstituted or substituted malonic dialkyl esters are described in the literature with the exception of the dimethyl ester of cyclohexene-l,l-dicarboxylic acid, b.p.: 70 to 72 0.; 11 14515.

The active ingredients are advantageously prepared in the presence of acid-binding agents, e.g., alkali metal carbonates, alcoholates, and hydroxides, and organic bases such as pyridine and trialkylamines. However, it is also possible to react preferably the alkali metal salts of the pyrazolidinediones with thionophosphoric ester halides of the above formula. The reaction is advantageously carried out in an inert organic solvent at a temperature of from 0 to 150 C., preferably from 30 to 130 C. Particularly suitable solvents are ketones, benzene, toluene, dioxane, nitriles such as acetonitrile and propionitrile, dimethylformamide, dimethyl sulfoxide and esters of organic acids. The yield may be increased by heating and stirring, after combining the starting materials, for a fairly long period of time at the prescribed temperature.

The thionophosphoric ester halides required as starting materials are known.

As a result of the variability of the malonic diesters and monoalkyl hydrazines used as starting materials it is possible to obtain numerous pyrazolidinediones bearing different substituents, whose phosphoric esters of the above formula have good insecticidal properties. The new thionophosphoric esters are generally colorless to reddish oils which are difiicultly soluble in water and are difiicult to distil even at considerable subatmospheric pressures without decomposition occurring. The compounds have an excellent action on a plurality of pests, and are there fore admirably suited for use as pesticides in the plant protection field.

The preparation and use of the new compounds are illustrated in the following examples.

The sodium salts of the pyrazolidinediones are obtained in good yields and high purity in the following manner. The hydrazides initially formed in the reaction of unsubstituted or substituted malonic diesters with hydrazine or substituted hydrazines are immediately cyclized with methanolic sodium methylate solution (technical grade); to complete the reaction, the mixture is boiled for some time under reflux. The sodium salts are soon precipitated or may, depending on the substituents, be isolated by removing the solvent in vacuo. It has been found to be advantageous to heat the salts freed from solvent for some time at 130 C.

The salts obtained in this way are sufiiciently pure for subsequent phosphorylation.

EXAMPLE 1 (a) 1-methyl-4,4-dimethylpyrazolidinedione-3,5 (sodium salt) 91.8 parts by weight of the dimethyl ester of dimethylmalonic acid is added to parts by weight of 31% by weight methanolic sodium methylate solution (technical grade) diluted with 100 parts by weight of methanol. While stirring this mixture, 26.4 parts by weight of methylhydrazine is then dripped in. The whole is heated for 3 hours under reflux and stirred overnight. The methanol is heating for 2 hours at 90 C. and a pressure of 0.5 mm.

Yield: 120 parts of orange-colored oil, r1 1.4829.

Analysis-Cale: C, 40.75; H, 6.51; N, 9.52; P, 10.51; S, 10.89. Found: C, 40.8; H, 6.7; N, 8.6; P, 10.7; S, 10.2.

then removed in a film evaporator and the residue kept for 5 The following compounds were prepared analogously:

N--NR' B O\fi /PO R 0 R R R. R R 11.,

CH: C Ha CH3 CH3 CH3 1. 4381 CH3 CH3 H CH3 CH3 CH3 CH2 CzHs CH3 CH3 CH3 CH3 i-CaH- CH3 CH3 CH: CH: Q CH: CH:

CH3 CHa OH: H CH3 CH3 CH3 CH3 H CH1! CH3 CH3 CH3 H CH; C-C2H5 CH; CH: CH: H CHr-CH2-OCH;

CH3 CH3 CH3 02H 02H CH CH3 OH; C2115 C2115 CH3 CH3 CzHls 02H: C2Hs CH3 CH3 CzHs C2115 i-C H CH3 CH3 0 2H5 C2 b Q 0 H3 CH3 C 2115 C 2H5 C H: C Ha H-C 3H7 C2115 C1115 CH3 C2115 C2115 C2H5 CzH5 CH3 C2Hs n-Oilil C2115 C2115 CH3 Il-C3H n-C3H CzH CzHs CH3 H-C4H9 l1-C4H0 C2H5 C2115 CH3 H CHz-O-CHQ C2135 C2 5 CH: =CH-O CzHs 1. 4945 02H; CzHs CH5 1. 4931 C 2H5 C 2115 Q CH3 C H:

02B; 02H, ('31 CH; CH;

3 hours at 130 C. The salt is then dried at 60 C. under The agents according to the invention may be used as an oil pump vacuum (0.5 mm. Hg). solutions, emulsions, suspensions 0r dusts. The form of Yield: approx. 90 parts by weight. application depends entirely on the purpose for which the All others salts may be prepared in analogous manner. agents are being used; in any case it should ensure a fine distribution of the active ingredient. (b) gggs h 'ga gg tg 232 2 3 dlazohdm For the preparation of the solutions to be sprayed direct, p p hydrocarbons having boiling points higher than 150 C., out w e.g. tetrahydronaphthalene or alkylated naphthalenes, or & organic liquids having boiling points higher than 150 C. kfi and having one or more than one functional group, e.g. P-O the keto group, the ether group, the ester group or the C2H5O/ amide group, this group or these groups being attached CH3 CH3 as substituent(s) to a hydrocarbon chain or being a component of a heterocyclic ring, may be used as spray liquids. 500 P i of aCetonltrlle is added 9 90 Parts y f l Aqueous formulations may be prepared from emulsion f the d Salt 9 Y y py f concentrates, pastes or wettable powders by adding water. -li the mlXmre heated Over P To prepare emulsions the ingredients as such or dissolved 0 minutes 1084. P f y welght 0f Qo-dlethyldl' in a solvent may be homogenized in Water or organic solthIOPhOSPhQIYI chlorlde 1S f pp f q e y, the vents by means of wetting or dispersing agents, e.g., polytemperature of the mixture 15 raised until it boils under ethylene oxide adducts. Concentrates which are suitable reflux; it is then kept for 16 hours at this temperature. for dil tion with water may be prepared from active in- The reaction mixture is then cooled to room temperature, gradient, emulsifying or dispersing agent and possibly the precipitated sodium chloride is removed by suction solvent. filtration and the solvent removed in vacuo. The residue Dusts may be prepared by mixing or grinding the active is taken up in benzene and washed with 100 parts by ingredients with a solid carrier, e.g., kieselguhr, talc, clay weight of water and then with 100 parts by weight of or fertilizers. 10% (by weight) aqueous NaHCO solution, the benzene The new active ingredients may be used by allowing an phase is removed and dried over Na SO the solvent is insecticidal amount of the compound to act on the insects removed and the residue freed from volatile impurities by or the objects to be protected against them, e.g., plants.

The compounds may be applied in conventional manner, e.g., by spraying, dusting, evaporating, atomizing or brushing.

EXAMPLE 2 90 parts by weight of the compound of Example 1 is mixed with parts by weight of N-methyl-u-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

EXAMPLE 3 20 parts by weight of the compound of Example 1 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 4 20 parts by weight of the compound of Example 1 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 5 20 parts by weight of the compound of Example 1 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280 C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 6 20 parts by weight of the compound of Example 1 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-e-sulfonic acid, 17 parts by weight of the sodium salt of a lignin sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquid is obtained containing 0.1% by weight of the active ingredient.

EXAMPLE 7 3 parts by weight of the compound of Example 1 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.

EXAMPLE 8 30 parts by weight of the compound of Example 1 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of parafiin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

To examine the insecticidal action of the new active ingredients, we selected the following compounds of the invention:

1 NNCH: QzHs-O S CzH5-0 CH: CH;

The following conventional compounds were used for comparison purposes:

(Phosalone) French Patent 1,482,025

/CH; J- CH N Diazinon) German Patent 910,652

EXAMPLE 9 Administration test on houseflies (Musca domestica) 1 mm. of an acetonic solution of the active ingredients is applied to the ventral abdomen of 4-day old housefies under slight CO narcosis. The mortality after 4 hours 7 8 EXAMPLE aqueous emulsions of the active ingredients are added.

Larvae in the 5th stage are then introduced into the veson 'n C u nous Contact expenmem onfimal sels. The mortality is determined after 24 hours.

cockroaches (Blatta Orientalis) Adult cockroaches are placed in l-liter beakers whose Concentration base and walls have been wetted with acetonic solutions ffigga figg of the active ingredients. After the solvent has evaporated, Active waterjparts Mortality the active ingredient remains as a thin layer. ingmdlent by weght) (percent) The action is determined after 48 hours. :33

1O 90 Amount of 30 active 95 Active ingredient Mortality 25 ingredient (mg./beaker) (percent) 0.01 80 We claimed: 3:3? 28 1. A dialkylthionophosphoric ester of the formula as "as NAT-R1 0.25 100 \H l 2.50 100 P O 0 1.00 30 R EXAMPLE 11 20 where R and R are identical or different and each de- Contact action on granary weevils (Sitophilus granarius) notes Iowa alkyl, denotes hydrogen, lower alkyl Pieces of glass (8 x 8 cm.) with a roughened surface phenyl or chlorophenyl, R and R are identical or difare treated with acetonic solutions of the active ingrediferent and each denotes lower alkyl, loweralkoxyrnethyl, ents. After the solvent has evaporated, 50 weevils are lower alkoxyethyl, or together denote lower alkoxymethplaced on this surface under a watch glass for 4 hours. ylene or pentamethylene. The weevils are then transferred to clean observation ves- 2. A clialkylthionophosphoric ester as claimed in claim sels. The mortality is determined after 24 hours and the 1 wherein R and R denote methyl or ethyl; and R R LD calculated therefrom. and R each denote methyl.

Active ingredient: 50 (mg) 3. A dialkylthionophosphoric ester as claimed in claim a 6 1 wherein R and R denote methyl or ethyl; R denotes Iv methyl, ethyl, propyl or isopropyl; and R and R denote methyl or ethyl. s (mfiecnve) 4. A dialkylthionophosphoric ester as claimed in claim 1 wherein R and R are methyl or ethyl; R is phenyl or EXAMPLE 1 chlorophenyl; and R and R are methyl. 7 t h th 5. A dialkylthionophosphoric ester as claimed in claim Action on g zgg l ii gi zsgg mo 40 1 wherein R and R are methyl or ethyl; R 15 methyl;

and R and R together denote a pentamethylene. I Young cabbage leaves are dipped into aqueous emul- 6 The compound mom of the active ingredients. After a short drying period caterpillars of the cabbage moth (4th larval stage) are placed on the leaves. The mortality is determined after (3,3543 5 48 hours. i o 0 o -0 i th? $13 0H: 0H, ingredient in Active emulsion Mortality ingredient p ce (pe ce 50 References Cited 1-32 :23 FOREIGN PATENTS 3-33 igg 713,278 8/1954 Great Britain 260-310 A 9,32 :33 OTHER REFERENCES 8:3? :33 Maguire et al., J. Chem. Soc. (London), 1958, pages 0.025 20 2299-2301.

EXAMPLE 13 NATALIE TROUSOF, Primary Examiner Action on larvae of the yellow fever CL X mosquito (Aedes aegypti) 260 310 B 424 400 200 ml. of boiled tap water is p ed i vesse s and 

1. A DIALKYLTHIONOPHOSPHORIC ESTER OF THE FORMULA 